CN115646540B - Composite hydrocracking catalyst, preparation method thereof and preparation method of transformer oil - Google Patents
Composite hydrocracking catalyst, preparation method thereof and preparation method of transformer oil Download PDFInfo
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Abstract
The invention belongs to the technical field of petrochemical industry, and particularly relates to a composite hydrocracking catalyst, a preparation method thereof and a preparation method of transformer oil. The composite hydrocracking catalyst is formed by compounding a catalyst A and a catalyst B according to a certain mass ratio; the catalyst A takes a Y molecular sieve and alumina as carriers, takes VIII and VIB metals as active metal components, the content of the alumina is 50-65wt%, the content of the Y molecular sieve is 10-40wt%, and the content of the active metal components is 10-35wt%; the catalyst B takes Beta molecular sieve and alumina as carriers, takes VIII and VIB metals as active metal components, the alumina content is 50-70wt%, the Beta molecular sieve content is 15-40wt%, and the active metal component content is 10-30wt%. The invention provides a composite hydrocracking catalyst which is used for preparing transformer oil and solves the problem that the conversion of alkane and arene cannot be considered.
Description
Technical Field
The invention belongs to the technical field of petrochemical industry, and particularly relates to a composite hydrocracking catalyst, a preparation method thereof and a preparation method of transformer oil.
Background
At present, the market of oil refining products is changed drastically, the demand of fuel oil, particularly aviation kerosene, is reduced rapidly, and oil refining enterprises are transformed to produce high added value products, so that the economic benefit of the enterprises is improved. The hydrocracking technology is used as a clean oil production technology, and can flexibly produce products such as light naphtha, jet fuel, diesel oil, transformer oil, industrial white oil, lubricating oil base oil, ethylene cracking raw materials and the like. With the increasing trend of integration of refining, hydrocracking technology plays a role as a regulator therein. In order to reduce the fuel oil yield, the hydrocracking device can be adjusted to produce high-added-value oil products such as transformer oil, industrial white oil, military aviation, ethylene cracking raw materials and the like, so that the method meets the market demands.
The transformer oil in the special oil product requires low aromatic hydrocarbon content and high isoparaffin content, while the conventional hydrocracking catalyst usually adopts a single molecular sieve component and an active metal component, so that the ring opening of aromatic hydrocarbon and the isomerism performance of the paraffinic hydrocarbon are difficult to be considered when wax oil, diesel oil and other fractions are processed, the problem that the conversion of the paraffinic hydrocarbon and the aromatic hydrocarbon cannot be considered cannot be solved, the produced transformer oil can be subjected to the problems of high aromatic hydrocarbon content or high pour point, and the prior art cannot directly produce transformer oil products when inferior raw oil is processed.
Therefore, a hydrocracking catalyst which has the advantages of taking account of aromatic ring opening and paraffin isomerization capability is developed to synchronously reduce the contents of aromatic hydrocarbon and normal paraffin in the transformer oil component produced by hydrocracking, so that a qualified transformer oil product is produced, and the method has important significance.
CN109794273B discloses a hydrotreating catalyst, which comprises an SB powder carrier, and Al, si, B, P, VIB group metal elements and VIII group metal elements supported on the carrier, and can be better used for preparing special transformer oil base oil without inhibitor with oxidation stability and gassing property, but the catalyst can only process special raw materials, reduce aromatic hydrocarbon in the raw materials, and cannot produce high-quality transformer oil with low pour point.
CN106867638A discloses a transformer oil composition, transformer oil and a method for preparing the same. The transformer oil composition comprises hyperbranched polyethylene base oil and additives, wherein the weight average molecular weight of the hyperbranched polyethylene is 250-1200, and the branching degree is 0.15-0.5. The transformer oil of the invention can ensure stable oil properties, uniform quality, high flash point, low pour point, good oxidation stability, gas-out property and heat conduction performance without adding viscosity index improver and pour point depressant, can meet the requirements of large capacity, common and ultra-high voltage grade and miniaturized power transformers, and can be used for a long time, but the method adopts an organic synthesis method to synthesize the transformer oil, and has high cost and low yield.
CN114410347a discloses a method for preparing low-aromatic transformer oil by medium-pressure hydrogenation of naphthenic base distillate oil. The naphthenic base distillate oil firstly enters a ring opening, isomerism pour point depressing and supplementary refining reaction zone after hydrodesulfurization, denitrification and dearomatization, and realizes selective ring opening of polycyclic compounds, isomerism of alkane (branched chain) and saturation of cracking olefin, and finally low-aromatic transformer oil distillate and clean light oil distillate are obtained. The method has the characteristics of simple process flow, small device investment scale, high operation safety, high yield of the base oil of the transformer oil, good product quality, environmental friendliness and the like, has a narrow application range, can only treat naphthenic base oil, and has pour points which are difficult to meet the product quality requirement when the paraffinic base oil is processed.
Disclosure of Invention
The invention aims to solve the technical problem of providing a composite hydrocracking catalyst which is used for preparing transformer oil and solves the problem that the conversion of alkane and arene cannot be considered; the invention also provides a preparation method of the composite hydrocracking catalyst.
The composite hydrocracking catalyst is formed by compounding a catalyst A and a catalyst B according to the mass ratio of (1:0.1) - (1:10), wherein the preferable mass ratio is (1:0.5) - (1:2); the catalyst A takes a Y molecular sieve and alumina as carriers, takes group VIII and VIB metals as active metal components, and takes the weight of the catalyst A as a reference, the content of the alumina is 50-65wt%, the content of the Y molecular sieve is 10-40wt%, and the content of the active metal components is 10-35wt% calculated by oxide; the catalyst B takes Beta molecular sieve and alumina as carriers, takes VIII and VIB metals as active metal components, takes the weight of the catalyst B as a reference, the content of the alumina is 50-70wt%, the content of the Beta molecular sieve is 15-40wt%, and the content of the active metal components is 10-30wt% calculated by oxide.
The active metal component of the VIII family in the catalyst A is Ni, and the active metal component of the VIB family is Mo; the active metal component of the catalyst A is 3-10wt% calculated by NiO and MoO 3 The calculated content is 7-25wt%; based on the weight of catalyst a.
The active metal component of the VIII family in the catalyst B is Co, and the active metal component of the VIB family is Mo; the content of the active metal component of the catalyst B is 3-10wt% calculated by CoO, calculated by MoO 3 The calculated content is 7-25wt%; based on the weight of catalyst B.
The preparation method of the catalyst A comprises the following steps: mechanically mixing a Y molecular sieve with alumina, adding an adhesive, rolling and forming, and then drying at 60-100 ℃ to obtain a catalyst carrier; and loading the active metal component on a catalyst carrier by adopting a solution impregnation method, drying at 60-100 ℃, and roasting at 450-600 ℃ to obtain the catalyst A.
The preparation method of the catalyst B comprises the following steps: mechanically mixing Beta molecular sieve and alumina, adding adhesive, rolling and forming, and drying at 60-100 ℃ to obtain a catalyst carrier; and loading the active metal component on a catalyst carrier by adopting a solution impregnation method, and drying at 60-100 ℃ and roasting at 450-600 ℃ to obtain the catalyst B.
The impregnation method is an isovolumetric impregnation method, an excessive volumetric impregnation method or a steam impregnation method.
The method for preparing the transformer oil by utilizing the composite hydrocracking catalyst comprises the following steps: raw oil and hydrogen are mixed and then sequentially pass through the upper part of the hydrofining reaction zone and the lower part of the hydrofining reaction zone; after the reaction, the mixture continuously enters a hydrocracking reaction zone to carry out arene ring opening and alkane isomerization reaction with a composite hydrocracking catalyst; and obtaining the product transformer oil and other byproducts after the hydrocracking reaction effluent passes through a separation system.
The reaction conditions of hydrofining and hydrocracking are as follows: the reaction pressure is 6.0-12.0 MPa; the hydrofining reaction temperature is 300-450 ℃; the hydrocracking reaction temperature is 320-460 ℃.
The raw oil is mixed oil of straight-run diesel oil and catalytic diesel oil, the initial distillation point is 120-250 ℃, the final distillation point is 310-380 ℃, and the density is 0.75-0.87 g/cm 3 The blending proportion of the catalytic diesel oil in the raw oil is 5-30%.
Filling hydrofining catalyst in the hydrofining reaction area with the airspeed of 0.2-3.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Filling a composite hydrocracking catalyst in a hydrocracking reaction zone, wherein the airspeed is 0.5-3.0 h -1 。
The upper part of the hydrofining reaction zone is filled with cobalt-molybdenum hydrofining catalyst, and the lower part of the reaction zone is filled with bulk hydrofining catalyst; the volume filling ratio of the upper catalyst to the lower catalyst in the hydrofining reaction zone is (1:0.2) - (1:5).
According to the method for preparing the transformer oil by utilizing the composite hydrocracking catalyst, raw oil and hydrogen are mixed and then enter a hydrofining reaction zone to contact with the hydrogenation catalyst, and denitrification, dearomatization and other impurity removal reactions are carried out; the effluent of the hydrofining reaction enters a hydrocracking reaction zone and a hydrocracking catalyst to carry out aromatic ring opening and paraffin isomerization reaction; the hydrocracking reaction effluent is separated to obtain transformer oil, light naphtha, heavy naphtha and other side products.
The cobalt-molybdenum type hydrofining catalyst filled in the upper part of the hydrofining reaction zone is a cobalt-molybdenum type hydrofining catalyst with strong capability of directionally saturating polycyclic aromatic hydrocarbon to monocyclic aromatic hydrocarbon, and can be commercial industrial hydrofining catalyst FHUDS-5 or FHUDS-7; or aluminum oxide is used as a carrier, co and Mo are used as active metals, and the self-control is carried out, and the preparation method comprises the following steps: firstly, uniformly mixing a carrier and an adhesive, fully rolling, forming, drying to obtain a catalyst carrier, and impregnating the catalyst carrier with a solution containing an active metal component, wherein the impregnation method can be an isovolumetric impregnation method, an excessive volumetric impregnation method, a steam impregnation method and the like, and drying at 60-100 ℃ and roasting at 450-600 ℃ to obtain the hydrofining catalyst. The mass fraction of the alumina is generally 50-85 wt%, preferably 60-75 wt%, based on the weight of the catalyst; the content of the active metal is 15-50wt% based on oxide, preferably 20-35wt%; wherein the mass fraction of cobalt species calculated by CoO is 3-12wt% calculated by MoO 3 The mass fraction of the calculated molybdenum is 12-40wt%.
The lower part of the hydrofining reaction zone is filled with a bulk phase hydrofining catalyst with strong single-ring aromatic hydrocarbon saturation capacity; for the commercial catalysts, FTX catalysts developed by the institute of petrochemical and Celestia catalysts developed by the company exkesen mobil are preferred.
The catalyst of the hydrofining reaction zone or the composite hydrocracking catalyst of the hydrocracking reaction zone has one or more of clover, cylinder, toothed sphere and the like.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the method for preparing the transformer oil, according to the reaction characteristics of the aromatic hydrocarbons with different ring numbers on the hydrofining catalysts of different types, the gradient deep saturation of the aromatic hydrocarbons is realized in a grading mode, and the purpose of reducing the aromatic hydrocarbons of the product to the maximum extent is achieved.
(2) By adopting the composite hydrocracking catalyst, the catalyst A loads nickel-molybdenum active metal on a Y molecular sieve, fully exerts the arene ring opening capability of the catalyst, and reduces the arene content of transformer oil in the process of producing transformer oil by catalytic cracking of raw oil; the catalyst B loads cobalt-molybdenum active metal on the Beta molecular sieve, enhances the adsorption and isomerization reaction of alkane, and reduces the pour point of transformer oil; after the composite catalytic reaction of the catalyst A and the catalyst B, the problem that the aromatic ring opening capability and the paraffin isomerization capability of the conventional hydrocracking catalyst are difficult to be compatible is solved.
(3) According to the invention, the hydrofining catalyst and the composite hydrocracking catalyst are adopted to prepare the transformer oil, so that the selective hydrogenation and directional conversion of the polycyclic aromatic hydrocarbon are realized, the hydrogen consumption of the device is low, the quality of the produced transformer oil is good, and the economic benefit of enterprises is effectively improved.
Detailed Description
The method for preparing transformer oil by using the composite hydrocracking catalyst provided by the invention will be further described below with reference to examples to compare effects and advantages of the hydrocracking method embodying the invention, but the invention is not limited thereto.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below, unless otherwise specified, were purchased from conventional biochemical reagent stores.
The raw oil used in the following examples and comparative examples was a mixed oil of catalytic diesel oil and straight-run diesel oil, in which the blending ratio of the catalytic diesel oil was 10%, and the properties thereof are shown in table 1. The properties of the catalysts used in the examples and comparative examples are shown in Table 2.
In the present invention, unless otherwise specified, percentages refer to mass fractions.
TABLE 1 raw oil Performance parameters
TABLE 2 Industrial catalyst Performance parameters
The refined oil refers to the effluent of the refining reactor, and the two hydrogen-oil ratios correspond to the inlet of the refining reactor and the inlet of the cracking reactor respectively.
Example 1
The preparation steps of the composite hydrocracking catalyst are as follows;
the preparation method of the catalyst A comprises the following steps: mechanically mixing 40wt% of Y molecular sieve with 50wt% of alumina, adding an adhesive, rolling and forming, and then drying at 90 ℃ to obtain a catalyst carrier; impregnating nickel-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of NiO is 3wt%, and MoO is adopted 3 The calculated content is 7wt%, and the catalyst A is obtained after drying at 70 ℃ and roasting at 550 ℃.
The preparation method of the catalyst B comprises the following steps: mechanically mixing 10wt% of beta molecular sieve with 70wt% of alumina, adding an adhesive, rolling and forming, and then drying at 80 ℃ to obtain a catalyst carrier; impregnating cobalt-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of the cobalt-molybdenum active metal is 10wt% calculated by CoO and MoO 3 The calculated content is 10wt%, and the catalyst B is obtained after drying at 70 ℃ and roasting at 550 ℃.
Finally, the catalyst A and the catalyst B are mechanically mixed according to the mass ratio of 1:0.1 to obtain the composite hydrocracking catalyst named HC-1.
The method for preparing the transformer oil by utilizing the composite hydrocracking catalyst comprises the following steps:
raw oil in table 1 and hydrogen are mixed and then sequentially enter the upper part of a hydrofining reaction zone, the upper part of the hydrofining reaction zone is filled with a hydrofining catalyst FHUDS-5, then the raw oil enters the lower part of the hydrofining reaction zone, the lower part of the hydrofining reaction zone is filled with hydrofining catalyst FTX, and the volume ratio of the two catalysts is 1:0.2; after the reaction, the catalyst enters a hydrocracking reaction zone, and carries out arene ring opening and paraffin isomerization reaction with the compound hydrocracking catalyst HC-1; and obtaining the product transformer oil and other byproducts after the hydrocracking reaction effluent passes through a separation system.
In the hydrocracking process, the reaction conditions of refining and cracking are as follows: the reaction pressure is 10.0MPa; the hydrofining reaction temperature is 400 ℃, and the volume space velocity of the hydrofining catalyst is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume space velocity of the hydrocracking catalyst is 1.5h -1 The refined oil (refining reactor effluent) had a nitrogen content of 10ppm, a hydrocracking conversion of 70%, a hydrofinishing/hydrocracking reactor inlet hydrogen to oil ratio of 600:1/800:1 and a run time of 2000 hours.
Example 2
The preparation steps of the composite hydrocracking catalyst are as follows;
the preparation method of the catalyst A comprises the following steps: mechanically mixing 10wt% of Y molecular sieve with 55wt% of alumina, adding an adhesive, rolling and forming, and then drying at 80 ℃ to obtain a catalyst carrier; impregnating nickel-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of NiO is 10wt% and MoO is adopted 3 The calculated content is 25wt%, and the catalyst A is obtained after drying at 70 ℃ and roasting at 550 ℃.
The preparation method of the catalyst B comprises the following steps: mechanically mixing 40wt% of beta molecular sieve with 50wt% of alumina, adding an adhesive, rolling and forming, and then drying at 70 ℃ to obtain a catalyst carrier; impregnating cobalt-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of the cobalt-molybdenum active metal is 3wt% calculated by CoO and MoO is adopted 3 The calculated content is 7wt%, and the catalyst B is obtained after drying at 70 ℃ and roasting at 550 ℃.
And finally, mechanically mixing the catalyst A and the catalyst B according to a mass ratio of 1:10 to obtain the composite hydrocracking catalyst, which is named HC-2.
The method for preparing the transformer oil by utilizing the composite hydrocracking catalyst comprises the following steps:
raw oil in table 1 and hydrogen are mixed and then sequentially enter the upper part of a hydrofining reaction zone, the upper part of the hydrofining reaction zone is filled with a hydrofining catalyst FHUDS-7, then the raw oil enters the lower part of the hydrofining reaction zone, the lower part of the hydrofining reaction zone is filled with hydrofining catalyst FTX, and the volume ratio of the two catalysts is 1:5; after the reaction, the catalyst enters a hydrocracking reaction zone, and carries out arene ring opening and paraffin isomerization reaction with the compound hydrocracking catalyst HC-2; the hydrocracking reaction effluent is separated to obtain transformer oil and other by-products.
In the hydrocracking process, the reaction conditions of refining and cracking are as follows: the reaction pressure is 10.0MPa; the hydrofining reaction temperature is 400 ℃, and the volume space velocity of the hydrofining catalyst is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume space velocity of the hydrocracking catalyst is 1.5h -1 The refined oil (refining reactor effluent) had a nitrogen content of 10ppm, a hydrocracking conversion of 70%, a hydrofinishing/hydrocracking reactor inlet hydrogen to oil ratio of 600:1/800:1 and a run time of 2000 hours.
Example 3
The preparation steps of the composite hydrocracking catalyst are as follows;
the preparation method of the catalyst A comprises the following steps: mechanically mixing 20wt% of Y molecular sieve with 65wt% of alumina, adding an adhesive, rolling and forming, and then drying at 80 ℃ to obtain a catalyst carrier; impregnating nickel-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of NiO is 5wt% and MoO is adopted 3 The calculated content is 10 weight percent, and the catalyst A is obtained after drying at 80 ℃ and roasting at 500 ℃.
The preparation method of the catalyst B comprises the following steps: mechanically mixing 15wt% of beta molecular sieve with 55wt% of alumina, adding an adhesive, rolling and forming, and then drying at 100 ℃ to obtain a catalyst carrier; impregnating cobalt-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of the cobalt-molybdenum active metal is 5wt% calculated by CoO and MoO 3 The calculated content is 25wt%, and the catalyst B is obtained after drying at 80 ℃ and roasting at 500 ℃.
And finally, mechanically mixing the catalyst A and the catalyst B according to a mass ratio of 1:2 to obtain the composite hydrocracking catalyst, which is named HC-3.
The method for preparing the transformer oil by utilizing the composite hydrocracking catalyst comprises the following steps:
raw oil in table 1 and hydrogen are mixed and then sequentially enter the upper part of a hydrofining reaction zone, the upper part of the hydrofining reaction zone is filled with a hydrofining catalyst FHUDS-5, then the raw oil enters the lower part of the hydrofining reaction zone, the lower part of the hydrofining reaction zone is filled with hydrofining catalyst FTX, and the volume ratio of the two catalysts is 1:3; after the reaction, the catalyst enters a hydrocracking reaction zone, and carries out arene ring opening and paraffin isomerization reaction with the compound hydrocracking catalyst HC-3; the hydrocracking reaction effluent is separated to obtain transformer oil and other by-products.
In the hydrocracking process, the reaction conditions of refining and cracking are as follows: the reaction pressure is 10.0MPa; the hydrofining reaction temperature is 400 ℃, and the volume space velocity of the hydrofining catalyst is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume space velocity of the hydrocracking catalyst is 1.5h -1 The nitrogen content of the refined oil is 10ppm, the hydrocracking conversion rate is 70%, the hydrogen-oil ratio at the inlet of the hydrofining/hydrocracking reactor is 600:1/800:1, and the running time is 2000h.
Example 4
The preparation steps of the composite hydrocracking catalyst are as follows;
the preparation method of the catalyst A comprises the following steps: mechanically mixing 30wt% of Y molecular sieve with 55wt% of alumina, adding an adhesive, rolling and forming, and then drying at 80 ℃ to obtain a catalyst carrier; impregnating nickel-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of NiO is 3wt%, and MoO is adopted 3 The calculated content is 12 weight percent, and the catalyst A is obtained after drying at 90 ℃ and roasting at 550 ℃.
The preparation method of the catalyst B comprises the following steps: mechanically mixing 20wt% of beta molecular sieve with 65wt% of alumina, adding an adhesive, rolling and forming, and then drying at 70 ℃ to obtain a catalyst carrier; impregnating cobalt-molybdenum active metal by adopting an isovolumetric impregnation method, wherein the content of the cobalt-molybdenum active metal is 3wt% calculated by CoO and MoO is adopted 3 The calculated content is 12 weight percent, and the catalyst B is obtained after drying at 80 ℃ and roasting at 500 ℃.
And finally, mechanically mixing the catalyst A and the catalyst B according to the mass ratio of 1:2 to obtain the composite hydrocracking catalyst, which is named HC-4.
The method for preparing the transformer oil by utilizing the composite hydrocracking catalyst comprises the following steps:
raw oil in table 1 and hydrogen are mixed and then sequentially enter the upper part of a hydrofining reaction zone, the upper part of the hydrofining reaction zone is filled with a hydrofining catalyst FHUDS-7, then the raw oil enters the lower part of the hydrofining reaction zone, the lower part of the hydrofining reaction zone is filled with hydrofining catalyst FTX, and the volume ratio of the two catalysts is 2:1; after the reaction, the catalyst enters a hydrocracking reaction zone, and carries out arene ring opening and paraffin isomerization reaction with the compound hydrocracking catalyst HC-4; the hydrocracking reaction effluent is separated to obtain transformer oil and other by-products.
In the hydrocracking process, the reaction conditions of refining and cracking are as follows: the reaction pressure is 10.0MPa; the hydrofining reaction temperature is 400 ℃, and the volume space velocity of the hydrofining catalyst is 1.0h -1 The method comprises the steps of carrying out a first treatment on the surface of the The volume space velocity of the hydrocracking catalyst is 1.5h -1 The nitrogen content of the refined oil is 10ppm, the hydrocracking conversion rate is 70%, the hydrogen-oil ratio at the inlet of the hydrofining/hydrocracking reactor is 600:1/800:1, and the running time is 2000h.
Comparative example 1
A method for preparing transformer oil by using a catalyst is exactly the same as in example 1, except that the upper part and the lower part of a hydrofining reaction zone are filled with a hydrofining catalyst FHUDS-5, a hydrocracking reaction zone is filled with an FC-52 hydrocracking catalyst developed by China petrochemical industry great company petrochemical industry research institute, and the other steps are the same, so as to prepare the transformer oil.
Comparative example 2
A method for preparing transformer oil by using a catalyst is exactly the same as in example 1, except that the upper part and the lower part of a hydrofining reaction zone are filled with a hydrofining catalyst FHUDS-7, a hydrocracking reaction zone is filled with an FC-52 hydrocracking catalyst developed by China petrochemical industry great company petrochemical industry research institute, and the other steps are the same, so as to prepare the transformer oil.
Comparative example 3
A method for preparing transformer oil by using a catalyst is completely the same as in example 1, except that industrial FHUDS-5 and FTX hydrofining catalyst are filled into a hydrofining reactor according to a filling volume ratio of 1:1, FC-52 hydrocracking catalyst developed by China petrochemical industry great company petrochemical industry research institute is filled into a hydrocracking reactor, and other steps are the same, so as to prepare the transformer oil.
Comparative example 4
A method for preparing transformer oil by using a catalyst is exactly the same as in example 1, except that an industrial FHUDS-7 hydrofining catalyst is filled into a hydrofining reactor, the HC-2 hydrocracking catalyst prepared in example 2 is filled into a hydrocracking reactor, and the other steps are the same, so as to prepare transformer oil.
Experimental results of the process for preparing transformer oil by hydrocracking of the above examples 1 to 4 are shown in table 3.
Table 3 experimental results of examples
Experimental results of the processes for preparing transformer oil by hydrocracking of the above comparative examples 1 to 4 are shown in table 4.
Table 4 results of experiments of comparative examples
As can be seen from the experimental results of the comparative example and the example, the hydrocracking method and the catalyst provided by the invention have the advantages that the hydrogen consumption is low, the aromatic hydrocarbon content and the pour point of the produced transformer oil are low, and the quality requirements of the transformer oil are all met under the condition of controlling the same conversion rate. When the catalyst grading system under the condition of example 2 is adopted, the content of polycyclic aromatic hydrocarbon in the produced transformer oil at 270-360 ℃ is the lowest, the pour point is the lowest, and the pour point is-15 ℃.
Of course, the foregoing is merely preferred embodiments of the present invention and is not to be construed as limiting the scope of the embodiments of the present invention. The present invention is not limited to the above examples, and those skilled in the art will appreciate that the present invention is capable of equally varying and improving within the spirit and scope of the present invention.
Claims (8)
1. A composite hydrocracking catalyst, characterized in that: is formed by compounding a catalyst A and a catalyst B according to the mass ratio of (1:0.1) - (1:10);
the catalyst A takes a Y molecular sieve and alumina as carriers, takes the metals of the VIII family and the VIB family as active metal components, and takes the weight of the catalyst A as a reference, the content of the alumina is 50 to 65 weight percent, the content of the Y molecular sieve is 10 to 40 weight percent, and the content of the active metal components is 10 to 35 weight percent calculated by oxide; the active metal component of the VIII family in the catalyst A is Ni, and the active metal component of the VIB family is Mo; the active metal component of the catalyst A is 3-10wt% calculated by NiO and MoO 3 The calculated content is 7-25 wt%; based on the weight of the catalyst A;
the catalyst B takes Beta molecular sieve and alumina as carriers, takes VIII and VIB metal as active metal components, takes the weight of the catalyst B as a reference, and has the alumina content of 50-70 wt%, the Beta molecular sieve content of 15-40 wt% and the active metal component content of 10-30 wt% calculated by oxide; the active metal component of the VIII family in the catalyst B is Co, and the active metal component of the VIB family is Mo; the active metal component of the catalyst B is 3-10wt% calculated by CoO and calculated by MoO 3 The calculated content is 7-25 wt%; based on the weight of catalyst B.
2. A method for preparing the composite hydrocracking catalyst as claimed in claim 1, characterized in that: the preparation method of the catalyst A comprises the following steps: mechanically mixing a Y molecular sieve with alumina, adding an adhesive, rolling and forming, and then drying at 60-100 ℃ to obtain a catalyst carrier; the active metal component is loaded on the catalyst carrier by adopting an impregnation method, and is dried at 60-100 ℃ and roasted at 450-600 ℃ to obtain the catalyst A.
3. The method for preparing the composite hydrocracking catalyst according to claim 2, characterized in that: the preparation method of the catalyst B comprises the following steps: mechanically mixing Beta molecular sieve with alumina, adding adhesive, rolling to form, and drying at 60-100 deg.c to obtain catalyst carrier; the active metal component is loaded on the catalyst carrier by adopting an impregnation method, and the catalyst B is obtained after drying at 60-100 ℃ and roasting at 450-600 ℃.
4. A method for preparing transformer oil by using the composite hydrocracking catalyst as claimed in claim 1, which is characterized in that: the method comprises the following steps: raw oil and hydrogen are mixed and then sequentially pass through the upper part of the hydrofining reaction zone and the lower part of the hydrofining reaction zone; after the reaction, the mixture continuously enters a hydrocracking reaction zone to carry out arene ring opening and alkane isomerization reaction with a composite hydrocracking catalyst; and obtaining the product transformer oil and other byproducts after the hydrocracking reaction effluent passes through a separation system.
5. The method for preparing transformer oil by using the composite hydrocracking catalyst according to claim 4, wherein: the reaction conditions of hydrofining and hydrocracking are as follows: the reaction pressure is 6.0-12.0 MPa; the hydrofining reaction temperature is 300-450 ℃; the hydrocracking reaction temperature is 320-460 ℃.
6. The method for preparing transformer oil by using the composite hydrocracking catalyst according to claim 4, wherein: the raw oil is mixed oil of straight-run diesel oil and catalytic diesel oil.
7. The method for preparing transformer oil by using the composite hydrocracking catalyst according to claim 4, wherein: filling hydrofining catalyst in hydrofining reaction zone with airspeed of 0.2-3.0 h -1 The method comprises the steps of carrying out a first treatment on the surface of the Filling a composite hydrocracking catalyst in a hydrocracking reaction zone, wherein the airspeed is 0.5-3.0 h -1 。
8. The method for preparing transformer oil by using the composite hydrocracking catalyst according to claim 4, wherein: the upper part of the hydrofining reaction zone is filled with cobalt-molybdenum hydrofining catalyst, and the lower part of the hydrofining reaction zone is filled with bulk hydrofining catalyst; the volume loading ratio of the catalyst at the upper part of the hydrofining reaction zone to the catalyst at the lower part of the hydrofining reaction zone is (1:0.2) - (1:5).
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| CN1493664A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Hydrocracking technology for increase production of low solidifying point diesel oil and ethylene producing raw material |
| CN1493667A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Hydrocracking process for maximally producing middle distillate |
| CN106675638A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation conversion process for catalytic diesel oil |
| CN114410347A (en) * | 2021-12-13 | 2022-04-29 | 中海油天津化工研究设计院有限公司 | Method for preparing low-aromatic transformer oil by medium-pressure hydrogenation of naphthenic base distillate oil |
| CN114437803A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating method for catalytic diesel oil |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1493664A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Hydrocracking technology for increase production of low solidifying point diesel oil and ethylene producing raw material |
| CN1493667A (en) * | 2002-11-02 | 2004-05-05 | 中国石油化工股份有限公司 | Hydrocracking process for maximally producing middle distillate |
| CN106675638A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Hydrogenation conversion process for catalytic diesel oil |
| CN114437803A (en) * | 2020-10-19 | 2022-05-06 | 中国石油化工股份有限公司 | Hydrotreating method for catalytic diesel oil |
| CN114410347A (en) * | 2021-12-13 | 2022-04-29 | 中海油天津化工研究设计院有限公司 | Method for preparing low-aromatic transformer oil by medium-pressure hydrogenation of naphthenic base distillate oil |
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